Ink jet ink set

ABSTRACT

An ink jet set comprising: a) a cyan ink comprising a carrier and a sulfonated copper phthalocyanine dye; b) a magenta ink comprising a carrier and an anthrapyridone magenta dye or metal complex magenta dye, or azo-naphthol derivative magenta dye or mixture thereof; c) a yellow ink comprising a carrier and an azo-aniline yellow dye or metal complex yellow dye or mixtures thereof; and d) a trisazo black dye of the following structure 
                         
where Met is a metal atom, preferably Al, Co, Cr, Cu, Fe, or Ni; R 1  is a phenyl or naphthalene radical substituted by 1, 2 or 3 substituents selected from the group consisting of OH, O(C1–C6)-alkyl, COOM, SO 3 M and NH 2 ; R 2  is C1–C6-alkyl, n is 0 or 1, X is a chemical bond or —CO— or —SO 2 —; R 3  is H, methyl or O(C1–C6)-alkyl; R 4  and R 5  are each H, COOM or SO 3 M; R 6  is a phenyl, pyridyl or pyrazole radical substituted by 1,2 or 3 substituents selected from the group consisting of OH, O(C1–C6)-alkyl, COOM, SO 3 M, NH 2 , NHaryl, NHacyl and phenylsulfo; and M is ammonium, H, K, Li, or Na.

CROSS REFERENCE TO RELATED APPLICATION

Reference is made to commonly assigned, co-pending U.S. patentapplication Ser. No. 10/695,165 by Blease et al., filed of even dateherewith entitled “Ink Jet Ink Set”.

FIELD OF THE INVENTION

This invention relates to inks for ink jet printing that provide imageswith good light fastness on laminated recording materials.

BACKGROUND OF THE INVENTION

Ink jet printing is a non-impact method for producing images by thedeposition of ink droplets in a pixel-by-pixel manner to animage-recording element in response to digital signals. There arevarious methods which may be utilized to control the deposition of inkdroplets on the image-recording element to yield the desired image. Inone process, known as continuous ink jet, a continuous stream ofdroplets is charged and deflected in an imagewise manner onto thesurface of the image-recording element, while unimaged droplets arecaught and returned to an ink sump. In another process, known asdrop-on-demand ink jet, individual ink droplets are projected as neededonto the image-recording element to form the desired image. Commonmethods of controlling the projection of ink droplets in drop-on-demandprinting include piezoelectric transducers and thermal bubble formation.Ink jet printers have found broad applications across markets rangingfrom industrial labeling to short run printing to desktop document andpictorial imaging.

The inks used in the various ink jet printers can be classified aseither dye-based or pigment-based. A dye is a colorant which isdissolved in the carrier medium. A pigment is a colorant that isinsoluble in the carrier medium, but is dispersed or suspended in theform of small particles, often stabilized against flocculation andsettling by the use of dispersing agents. The carrier medium can be aliquid or a solid at room temperature in both cases. Commonly usedcarrier recording materials include water, mixtures of water and organicco-solvents and high boiling organic solvents, such as hydrocarbons,esters, ketones, etc.

For aqueous dye-based inks, the dyes needs to be sufficiently soluble inwater to prepare a solution that is capable of producing adequatedensity on the receiving element and stable for extended periods ofstorage without precipitation. High quality ink jet printing withdye-based inks requires dyes which will provide both bright hue and goodlight fastness.

To generate full color prints via ink jet printing, ink sets comprisingat least cyan, magenta and yellow inks are normally utilized. Inaddition a black ink is often added to enhance the printing of text anddarker colors. The range of colors that can be produced with a given setof inks defines the color gamut of that ink set. For the production ofhigh quality photorealistic images via ink jet printing, ink sets with alarge color gamut are preferred. In addition, it is important that theink sets produce images with good fastness, especially to light.

The choice of the colorants in ink jet systems is critical for bothlight fastness and color gamut. The color gamut of an ink set iscontrolled primarily by the spectral absorption characteristics of thecomponent dyes. The primary dyes (e.g., cyan, magenta and yellow) shouldonly absorb light of the required wavelengths (i.e., have relativelynarrow absorption bands) and not overlap excessively with the dyes inthe complementary inks. In addition to the light absorptioncharacteristics of the dyes, the maximum print density achieved from theink is another important factor to provide a high color gamut. Thehigher the print density the greater the color gamut.

Of particular importance is the light fastness of the component dyeswhen printed on recording materials which are subsequently sealed with alaminating film. Lamination is done to protect the printed image fromphysical damage and also to further enhance the stability of the printedimage against light fade and fade due to environmental pollutants suchas ozone.

Recording material laminate films are available in a variety of formsand can be categorized on their mode of adhesion to the printedrecording material. These forms include heat activated laminates,thermal laminates and pressure sensitive laminates. Laminate films cancontain ultraviolet light absorbing compounds which can in part protectthe printed dyes from fade due to ultraviolet light.

Numerous dye based ink jet ink sets have been described in patentliterature. For example, U.S. Pat. No. 6,152,969 relates to a set ofinks comprising C.I. Direct Blue 199, C.I. Direct Yellow 86 and ananthrapyridone magenta dye however no mention is made of a suitableblack dye for the ink jet ink set. U.S. Pat. No. 6,183,548 B1 related toa set of inks comprising Direct Yellow 107, Direct Yellow 132 or DirectYellow 86, a water soluble, transition metal complex of an8-hetercyclylazo-5-hydroquinoline dye, a sulfonated copperphthalocyanine dye and black dyes selected from Reactive Black 31,Direct Black 19, Direct Black 168 or Solubilized Sulfur Black 1. PatentApplication EP 1,167,472 discloses an ink jet ink set comprising C.I.Direct Blue 199, Ilford M-377 magenta dye (CAS # 182061-89-8) in amagenta dye mixture with C.I. Acid Red 52, C.I. Direct Yellow 132 andC.I. Food Black 2.

U.S. Pat. No. 5,725,641 describes Reactive Black 31, a disazo metal(specifically copper) complex dye as unsuitable for ink jet inkcompositions since at neutral pH it hydrolyzes over time causing the inkpH to drop and an increase in sulfonate ions. This can be detrimental tometal surfaces in the ink jet print head due to corrosion resulting fromthe acidic pH and increased ion content. Direct Black 19 exhibits severebronzing (a metallic like reflection) on several types of ink jet inkreceiving media. Direct Black 168 and Food Black 2 both exhibitunacceptable light fastness when compared to the other dyes in an inkjet ink set. U.S. Pat. No. 4,343,653 states that because of hydrolysisof the thiosulfonate salt group, Solubilized Sulfur Black 1 will slowlyprecipitate from the ink and will likely result in clogging of the printhead nozzles. What is needed then is an ink jet ink set comprising cyan,magenta, yellow and black inks all having good light fastness onlaminated media and without the physical and chemical problems of blackdyes previously included in ink jet ink sets.

U.S. patent application Publication 2001/0027734A1 describes blacktrisazo metal complex dyes for use in ink jet ink sets but preferredcyan, magenta and yellow dyes are not described, in particular for theirability to provide acceptable light fastness on laminated ink jetreceivers.

It is an object of this invention to provide an ink set capable ofproducing images with high light fastness when printed on laminatedrecording materials.

SUMMARY OF THE INVENTION

The present invention discloses a color ink jet set for color printingcomprising:

-   -   a) a cyan ink comprising a carrier and a sulfonated copper        phthalocyanine dye;    -   b) a magenta ink comprising a carrier and an anthrapyridone        magenta dye or metal complex magenta dye, azo-naphthol        derivative magenta dye or mixture thereof;    -   c) a yellow ink comprising a carrier and an azoaniline yellow        dye or metal complex yellow dye or mixtures thereof; and    -   d) a trisazo black dye of the follow structure

where

-   -   Met is a metal atom, preferably Al, Co, Cr, Cu, Fe, or Ni;    -   R₁ is a phenyl or naphthalene radical substituted by 1, 2 or 3        substituents selected from the group consisting of OH, O(C1–C6)        alkyl, COOM, SO₃M and NH₂;    -   R₂ is C1–C6 alkyl, n is 0 or 1, X is a chemical bond or —CO— or        —SO₂—;    -   R₃ is H, methyl or O(C1–C6) alkyl;    -   R₄ and R₅ are each H, COOM or SO₃M;    -   R₆ is a phenyl, pyridyl or pyrazole radical substituted by 1,2        or 3 substituents selected from the group consisting of OH,        O(C1–C6) alkyl, COOM, SO₃M, NH₂, NHaryl, NHacyl and phenylsulfo;        and    -   M is ammonium, H, K, Li, or Na, as described in U.S. patent        application Publication No. 2001/0027734A1, at page 2, the        disclosure of which is incorporated herein by reference.

An ink jet ink set comprising the above cyan, magenta, yellow and blackdyes provides excellent light fastness on laminated ink jet receiverswhile simultaneously avoiding the above problems described with othertypes of black dyes.

DETAILED DESCRIPTION OF THE INVENTION

Any copper phthalocyanine cyan dye or mixture thereof may be used in thecyan ink. In a preferred embodiment the cyan dye is C. I. Direct Blue86, C. I. Direct Blue 199, Bayer Bayscript® BA, BASF Basacid® 762, or C.I. Direct Blue 307 (available as Avecia Pro-Jet® Fast Cyan 2).

Any metal complex magenta dye or anthrapyridone magenta dye orazo-naphthol derivative magenta dye or mixtures thereof may be used inthe magenta ink. In a preferred embodiment the metal complex magenta dyeis Kodak Lightfast Magenta 1 (CAS # 251959-65-6), C. I. Reactive Red 23,or pacified C. I. Reactive Red 23, the azo-naphthol derivative magentadye is C. I. Reactive Red 31, pacified Reactive Red 31, or IlfordMagenta M-377 (CAS # 182061-89-8), and the anthrapyridone magenta dye isNippon Kayaku JPD EK-1 (CAS# 224628-70-0), Acid Red 80, Acid Red 82 orCAS# 212080-60-9.

Any azo-aniline yellow dye or metal complex yellow dye or mixturesthereof may be used in the yellow ink. In a preferred embodiment theyellow azo-aniline dye is C.I. Direct Yellow 86, C.I. Direct Yellow 107,C. I. Direct Yellow 132, or C. I. Direct Yellow 173 and the yellow metalcomplex yellow dye is C.I. Acid Yellow 99 or C. I. Acid Yellow 114.

Any trisazo metal complex black dye or mixtures thereof may be used inthe black ink. In a preferred embodiment, the trisazo dye is ClariantDuasyn® Black NB-SF. The black ink may also be adjusted for color byaddition of a copper phthalocyanine cyan dye, a metal complex magentadye, an anthrapyridone magenta dye, an azo-naphthol derivative magentadye, an azo-aniline yellow dye, a metal complex yellow dye, an orangedye, a green dye, a violet dye or mixtures thereof.

In general, the inks of this invention comprise the above dyes atconcentrations of 0.1 to 15%, preferably 0.4% to 6% by weight of the inkjet ink composition.

The ink jet ink may further comprise a light cyan ink and a lightmagenta ink. The light cyan ink may comprise a carrier and a sulfonatedcopper phthalocyanine dye. More specifically the light cyan ink maycomprise a carrier and C. I. Direct Blue 86, C. I. Direct Blue 199, orC. I. Direct Blue 307 or mixtures thereof. The light magenta ink maycomprise a carrier and an anthrapyridone magenta dye or metal complexmagenta dye or azo-naphthol derivative magenta dye or mixture thereofmixture thereof. More specifically the light magenta ink may comprise acarrier and Kodak Lightfast Magenta 1 (CAS # 251959-65-6), C. I.Reactive Red 23, pacified C. I. Reactive Red 23, C. I. Reactive Red 31,pacified C. I. Reactive Red 31, CAS #182061-89-8, Acid Red 80, Acid Red82, Nippon Kayaku JPD EK-1 (CAS# 224628-70-0) or CAS# 212080-60-9 ormixtures thereof. The ink jet ink set may further comprise a lightyellow ink. The light yellow ink may comprise a carrier and anazoaniline yellow dye or metal complex yellow dye or mixtures thereof.More specifically the light yellow ink may comprise a carrier and C.I.Direct Yellow 86, C.I. Direct Yellow 107, C. I. Direct Yellow 132, or C.I. Direct Yellow 173 and the yellow metal complex yellow dye is C.I.Acid Yellow 99 or C. I. Acid Yellow 114 or mixtures thereof. The ink setmay further comprise a light black (gray) ink comprising a carrier and atrisazo metal complex black dye, a carbon black pigment, aself-dispersing carbon black pigment or mixtures thereof.

A humectant is usually employed in the ink jet compositions of theinvention to help prevent the ink from drying out or crusting in theorifices of the print head. Examples of humectants which can be usedinclude polyhydric alcohols, such as ethylene glycol, diethylene glycol(DEG), triethylene glycol, propylene glycol, tetraethylene glycol,polyethylene glycol, glycerol, 2-methyl-2,4-pentanediol,2-ethyl-2-hydroxymethyl-1,3-propanediol (EHMP), 1,5 pentanediol,1,2-hexanediol, 1,2,6-hexanetriol; lower alkyl mono- or di-ethersderived from alkylene glycols, such as ethylene glycol mono-methyl ormono-ethyl ether, diethylene glycol mono-methyl or mono-ethyl ether,propylene glycol mono-methyl or mono-ethyl ether, triethylene glycolmono-methyl, mono-ethyl or mono-butyl ether (TEGMBE), diethylene glycoldi-methyl or di-ethyl ether, poly(ethylene glycol) monobutyl ether(PEGMBE), and diethylene glycol monobutylether (DEGMBE);nitrogen-containing compounds, such as urea, pyrrolidin-2-one,N-methyl-pyrrolidin-2-one, and 1,3-dimethyl-2-imidazolidinone; andsulfur-containing compounds such as dimethyl sulfoxide, thioglycol, andtetramethylene sulfone.

Preferred humectants for the inks of the invention include DEG,glycerol, DEGMBE, TEGMBE, 1,2-hexanediol, 1,5-pentanediol, urea,pyrrolidin-2-one, EHMP and mixtures thereof. The humectant may beemployed in each ink in an amount of from about 5 to about 60 weightpercent of the ink composition.

Water-miscible organic solvents may also be added to the aqueous inks ofthe invention to help the ink penetrate the receiving substrate,especially when the substrate is a highly sized paper. Examples of suchsolvents include alcohols, such as methyl alcohol, ethyl alcohol,n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol,t-butyl alcohol, iso-butyl alcohol, furfuryl alcohol, andtetrahydrofurfuryl alcohol; ketones or ketoalcohols such as acetone,methyl ethyl ketone and diacetone alcohol; ethers, such astetrahydrofuran and dioxane; and esters, such as, ethyl lactate,ethylene carbonate and propylene carbonate.

The amount of aqueous carrier employed is in the range of approximately40 to 98 weight %, preferably approximately 70 to 98 weight %, based onthe total weight of the ink. A mixture of water and a polyhydricalcohol, such as diethylene glycol, is useful as an aqueous carrier. Ina preferred embodiment, the inks contain from about 5 to about 60 weight% of water miscible organic solvent. More preferably, the ink containsfrom about 10% to about 35% of water miscible organic solvent.Percentages are based on the total weight of the aqueous carrier. In oneembodiment the concentration of organic solvents and humectants is 5% to50% by weight and water is 50% to 95% by weight.

Surfactants may be added to the ink to adjust the surface tension to anappropriate level. The surfactants may be anionic, cationic, amphotericor nonionic and used at levels of 0.01 to 1% of the ink composition.Preferred surfactants include Surfynol® 465 (available from Air ProductsCorp.) and Tergitol® 15-S-5 (available from Union Carbide).

A biocide may be added to the ink composition employed in the inventionto suppress the growth of microorganisms such as molds, fungi, etc. inaqueous inks. A preferred biocide for the ink composition employed inthe present invention is Proxel® GXL (Avecia Corp.) at a finalconcentration of 0.0001–0.5 wt. %.

The pH of the aqueous ink compositions employed in the invention may beadjusted by the addition of organic or inorganic acids or bases. Usefulinks may have a preferred pH of from about 2 to 10, depending upon thetype of dye or pigment being used. Typical inorganic acids includehydrochloric, phosphoric and sulfuric acids. Typical organic acidsinclude methanesulfonic, acetic and lactic acids. Typical inorganicbases include alkali metal hydroxides and carbonates. Typical organicbases include ammonia, triethanolamine and tetramethylethlenediamine.

A typical ink composition employed in the invention may comprise, forexample, the following components by weight: colorant (0.1–15%), water(20–95%), humectants (5–70%), water miscible co-solvents (2–20%),surfactants (0.1–10%), biocide (0.05–5%) and pH control agents(0.1–10%).

Additional additives which may optionally be present in the ink jet inkcompositions employed in the invention include thickeners, conductivityenhancing agents, anti-kogation agents, drying agents, defoamers,anti-corrosion aids, viscosity modifying polymers, or sequestrants.

The ink jet inks provided by this invention may be employed in ink jetprinting wherein liquid ink drops are applied in a controlled fashion toan ink receptive layer substrate, by ejecting ink droplets from aplurality of nozzles or orifices of the print head of an ink jetprinter.

Commercially available ink jet printers use several different schemes tocontrol the deposition of the ink droplets. Such schemes are generallyof two types: continuous stream and drop-on-demand.

In drop-on-demand systems, a droplet of ink is ejected from an orificedirectly to a position on the ink receptive layer by pressure createdby, for example, a piezoelectric device, an acoustic device, or athermal process controlled in accordance digital data signals. An inkdroplet is not generated and ejected through the orifices of the printhead unless it is needed. Ink jet printing methods, and relatedprinters, are commercially available and need not be described indetail.

Ink jet inks of the present invention can be used in any of the popularink jet printing systems, including thermal or piezoelectricdrop-on-demand printers and continuous ink jet printers. Of course, thespecific ink formulations will vary depending upon the type of ink jetprinting system.

Ink-receptive substrates useful in ink jet printing are well known tothose skilled in the art. Representative examples of such substrates aredisclosed in U.S. Pat. Nos. 5,605,750; 5,723,211; and 5,789,070 and EP813 978 A1, the disclosures of which are hereby incorporated byreference.

The following example illustrates the utility of the present invention.

EXAMPLES Preparation of Inks

Inks used in the invention and control inks were prepared by simplemixing of the ingredients. After thorough mixing, each ink was filteredwith a 0.2 micron filter. The inks shown in table 1 were prepared.

TABLE 1 weight % ink # color dye class dye dye in ink 1 cyan copperphthalocyanine Direct Blue 199^(a) 3.50 2 cyan copper phthalocyanineDirect Blue 307^(b) 3.50 3 magenta anthrapyridone Nippon Kayaku 4.00 JPDEK-1^(c) 4 magenta anthrapyridone Acid Red 82^(d) 4.00 5 magentaazo-naphthol Magenta M-377^(e) 4.00 6 magenta metal complex Reactive Red23^(f) 4.00 7 magenta metal complex Kodak Light Fast 1.00 Magenta 1^(g)8 yellow azoaniline Direct Yellow 132^(h) 2.75 9 yellow azoanilineDirect Yellow 86^(i) 2.75 10 yellow metal complex Duasyn ® GF-SF^(j)2.75 11 black tris azo metal complex Duasyn ® NB-SF^(k) 4.00^(a)available as Duasyn ® Direct Turquoise Blue FRL Liquid from ClariantCorp., a 10 wt. % dye solution in water ^(b)available as Pro-Jet ® FastCyan 2 from Avecia Inc., a 6 wt. % dye solution in water ^(c)availableas a 10 wt. % dye solution in water from Nippon Kayaku Kabushiki Kaisha^(d)available as a 10 wt. % dye solution in water from Bayer Corp.^(e)available as a dry solid from Ilford Imaging Switzerland, GmbH^(f)available as Duasyn ® 3B-SF Liquid from Clariant Corp., a 15 wt. %dye solution in water ^(g)available as a 5 wt % dye solution in waterfrom Eastman Kodak Co. ^(h)available as Pro-Jet ® Yellow 1G from Avecia,Inc., a 7.5 wt. % dye solution in water ^(i)available as a 10 wt. % dyesolution in water from Sensient Technical Colors, Inc. ^(j)available asa 4 wt. % dye solution in water from Clariant Corp. ^(k)available as a20 wt. % dye solution in water from Clariant Corp.

Due to the relatively high mass absorptivity of the Kodak Light FastMagenta 1 dye, only 1 wt. % was needed in the magenta ink to achievesatisfactory image density. In addition to the dyes, all of the inks intable 1 were prepared with 23 wt. % glycerol, 7.0 wt % triethyleneglycol mono-butyl ether, 0.3 wt. % triethanolamine and 0.09 wt. % lacticacid with the balance being water.

As comparative examples, the inks in table 2 were prepared.

TABLE 2 ink # color dye weight % dye C-1 cyan Acid Blue 9^(l) 3.50 C-2magenta Acid Red 52^(m) 4.00 C-3 yellow Acid Yellow 23^(n) 2.75 C-4black Food Black 2^(o) 4.00 C-5 black Direct Black 168^(p) 4.00^(l)available from Sensient Technical Colors as a 10 wt. % dye solutionin water ^(m)available from Sensient Technical Colors as a 10 wt. % dyesolution in water ^(n)available as Pro-Jet ® Yellow OAM from Avecia,Inc., a 7.5 wt. % dye solution in water ^(o)available from SensientTechnical Colors as a 10 wt. % dye solution in water ^(p)available asPro-Jet ® Direct Black 168 from Avecia, Inc., a 10 wt. % dye solution inwater

In addition to the dyes, all of the inks in table 2 were prepared with23 wt. % glycerol, 7.0 wt % triethylene glycol mono-butyl ether, 0.3 wt.% triethanolamine and 0.09 wt. % lactic acid with the balance beingwater.

To evaluate the inks of the invention and the comparative inks, each inkwas placed in an ink cartridge for a Canon Model S520 printer andprinted using the Canon model S520 printer. A density scale was createdby printing areas at 10%, 25%, 40%, 50%, 75% and 100% dot coverage. Theinks of the invention and the comparative inks were printed onto KodakInstant Dry Glossy media and Ilford Instant Dry (IDP1GP9) media.Approximately 1 day after printing, the printed media were laminatedusing Kodak Pro-Lustre lamination film.

Each density patch was measured for The Status A visual, red, green andblue densities using a MacBeth-Gretag Spectrolino densitometer. TheKodak media and Ilford media were read in reflection mode. Aftermeasuring, the printed and laminated media were exposed to 50 kLuxsimulated daylight radiation for two weeks. High intensity exposure suchas this is intended to provide an accelerated response to normal useconditions wherein the light exposure is of much lower intensity but theexposure is for a much longer duration. It is desired for each ink ofthe ink set to fade less than about 30% in density from a startingdensity of 1.0 on one or both of the media types used to evaluate theinks. Each density patch was then re-read after the high intensityexposure to assess the light fastness of each density patch. For cyaninks, the change in Status A red density was recorded, for the magentainks the change in Status A green density was recorded, for the yellowinks the change in Status A blue density was recorded and for the blackinks, the change in Status A visual density was recorded. The percentchange in density from an initial starting density of 1.0 was determinedby linear interpolation between areas with starting densities which wereless than and greater than 1.0 density. Inks having less than about 10%fade are indicated with an A rating, from 10% fade to less than about20% fade a B rating, from 20% fade to less than about 30% fade a Crating and 30% or more fade a D rating. The results for the inks of theinvention and the comparative examples are shown in table 3.

TABLE 3 % density loss after 2 weeks exposure at 50 kLux daylight Ink #Kodak Instant Dry Glossy media Ilford Instant Dry media  1 B A  2 B A  3B C  4 C C  5 B C  6 B D  7 B B  8 C A  9 B A 10 B B 11 A A C-1 D D C-2D D C-3 D D C-4 D D C-5 D D

The inks of the invention set all show percent fade values from aninitial density of 1.0 or less than about 30% on at least one of themedia types. Thus an ink jet set comprising a cyan, magenta, yellow andblack ink selected from among the inks of the invention will providelaminated prints with only slight color shifts due to light fade. Inaddition, the black ink comprising a trisazo metal complex black dye didnot show any bronzing on printing and was pH stable (unlike the pHinstability with the bisazo metal complex dye Reactive Black 31 asdiscussed in U.S. Pat. No. 5,725,641).

The comparative inks all show unacceptable fade which if used in an inkjet ink set would result in objectionable losses in print density andobjectionable colors shifts (due to non-uniform fade among the inks)from exposure to light over time.

The invention has been described in detail with particular reference touseful embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

1. An ink jet set comprising: A) a cyan ink comprising a carrier and asulfonated copper phthalocyanine dye; B) a magenta ink comprising acarrier and an anthrapyridone magenta dye; C) a yellow ink comprising acarrier and an azo-aniline yellow dye or metal complex yellow dye ormixtures thereof; and D) a black ink comprising a trisazo black dye ofthe following structure

where Met is a metal atom; R₁ is a phenyl or naphthalene radicalsubstituted by 1, 2 or 3 substituents selected from the group consistingof OH, O(C1–C6)-alkyl, COOM, SO₃M and NH₂; R₂ is C1–C6-alkyl, n is 0 or1, X is a chemical bond or —CO— or —SO₂—; R₃ is H, methyl orO(C1–C6)-alkyl; R₄ and R₅ are each H, COOM or SO₃M; R₆ is a phenyl,pyridyl or pyrazole radical substituted by 1,2 or 3 substituentsselected from the group consisting of OH, O(C1–C6)-alkyl, COOM, SO₃M,NH₂, NHaryl, NHacyl and phenylsulfo; and M is ammonium, H, K, Li, or Na.2. An ink jet ink set according to claim 1 wherein the dye in each inkis present in the ink in a concentration of 0.1% to 15% by weight of theink composition.
 3. An ink jet ink set according to claim 1 wherein thecyan ink comprises a carrier and C. I. Direct Blue 86, C. I. Direct Blue199, or C. I. Direct Blue 307 or mixtures thereof.
 4. An ink jet ink setaccording to claim 1 wherein the magenta ink comprises a carrier andCAS# 224628-70-0, Acid Red 80, Acid Red 82, or CAS# 212080-60-9 ormixtures thereof.
 5. An ink jet ink set according to claim 1 wherein theyellow ink comprises a carrier and C.I. Direct Yellow 86, C.I. DirectYellow 107, C. I. Direct Yellow 132, or C. I. Direct Yellow 173 and theyellow metal complex yellow dye is C.I. Acid Yellow 99 or C. I. AcidYellow 114 or mixtures thereof.
 6. An ink jet ink set according to claim1 wherein the ink set further comprises a light cyan ink and a lightmagenta ink.
 7. An ink jet ink set according to claim 6 wherein thelight cyan ink comprises a carrier and a sulfonated copperphthalocyanine dye.
 8. An ink jet ink set according to claim 7 whereinthe light cyan ink comprises a carrier and C. I. Direct Blue 86, C. I.Direct Blue 199, or C. I. Direct Blue 307 or mixtures thereof.
 9. An inkjet ink set according to claim 6 wherein the light magenta ink comprisesa carrier and an anthrapyridone magenta dye or metal complex magenta dyeor azo-naphthol derivative magenta dye or mixture thereof mixturethereof.
 10. An ink jet ink set according to claim 9 wherein the lightmagenta ink comprises a carrier and Acid Red 80, Acid Red 82, (CAS#224628-70-0) or CAS# 212080-60-9 or mixtures thereof.
 11. An ink jet inkset according to claim 6 wherein the ink set further comprises a lightyellow ink.
 12. An ink jet ink set according to claim 11 wherein thelight yellow ink comprises a carrier and an azoaniline yellow dye ormetal complex yellow dye or mixtures thereof.
 13. An ink jet ink setaccording to claim 12 wherein the yellow ink comprises a carrier andC.I. Direct Yellow 86, C.I. Direct Yellow 107, C. I. Direct Yellow 132,or C. I. Direct Yellow 173 and the yellow metal complex yellow dye isC.I. Acid Yellow 99 or C. I. Acid Yellow 114 or mixtures thereof.
 14. Anink jet ink set according to claim 11 wherein the ink set furthercomprises a light black (gray) ink comprising a carrier and a trisazometal complex black dye, a carbon black pigment, a self-dispersingcarbon black pigment or mixtures thereof.
 15. An ink jet ink setaccording to claim 1 wherein the carrier comprises water and watersoluble organic solvents, humectants or a combination thereof.
 16. Anink jet ink set according to claim 5 wherein the humectants are selectedfrom the group consisting of glycerol, diethylene glycol, diethyleneglycol monobutyl ether, triethylene glycol monobutyl ether,2-pyrrolidinone, urea and mixtures thereof.
 17. An ink jet ink setaccording to claim 15 wherein the concentration of organic solvents, andhumectants is 5% to 50% by weight and water is 50% to 95% by weight. 18.An ink jet ink set according to claim 16 wherein the carrier furthercomprises a non-ionic surfactant.
 19. An ink jet printing method,comprising the steps of: A) providing an ink jet printer that isresponsive to digital data signals; B) loading said printer with an inkjet recording element comprising a support having thereon animage-receiving layer; C) loading said printer with an ink jet ink setcomprising: a) a cyan ink comprising a carrier and a sulfonated copperphthalocyanine dye; b) a magenta ink comprising a carrier and ananthrapyridone magenta dye; c) a yellow ink comprising a carrier and anazo-aniline yellow dye or metal complex yellow dye or mixtures thereof;and d) a black ink comprising a trisazo black dye of the followingstructure

where Met is a metal atom; R₁ is a phenyl or naphthalene radicalsubstituted by 1, 2 or 3 substituents selected from the group consistingof OH, O(C1–C6)-alkyl, COOM, SO₃M and NH₂; R₂ is C1–C6-alkyl, n is 0 or1, X is a chemical bond or —CO— or —SO₂—; R₃ is H, methyl orO(C1–C6)-alkyl; R₄ and R₅ are each H, COOM or SO₃M; R₆ is a phenyl,pyridyl or pyrazole radical substituted by 1,2 or 3 substituentsselected from the group consisting of OH, O(C1–C6)-alkyl, COOM, SO₃M,NH₂, NHaryl, NHacyl and phenylsulfo; and M is ammonium, H, K, Li, or Na;and D) printing on said image-receiving layer using said ink jet ink setin response to said digital data signals.